CN110064309B - Composite membrane for MABR and preparation method thereof - Google Patents

Composite membrane for MABR and preparation method thereof Download PDF

Info

Publication number
CN110064309B
CN110064309B CN201910296974.1A CN201910296974A CN110064309B CN 110064309 B CN110064309 B CN 110064309B CN 201910296974 A CN201910296974 A CN 201910296974A CN 110064309 B CN110064309 B CN 110064309B
Authority
CN
China
Prior art keywords
membrane
mabr
composite
polyvinylidene fluoride
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910296974.1A
Other languages
Chinese (zh)
Other versions
CN110064309A (en
Inventor
张磊
魏春飞
赵勇娇
王允妹
单连斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang Academy Environmental Sciences
Original Assignee
Shenyang Academy Environmental Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang Academy Environmental Sciences filed Critical Shenyang Academy Environmental Sciences
Priority to CN201910296974.1A priority Critical patent/CN110064309B/en
Publication of CN110064309A publication Critical patent/CN110064309A/en
Application granted granted Critical
Publication of CN110064309B publication Critical patent/CN110064309B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention relates to the technical field of an MABR composite membrane, in particular to a composite membrane for MABR and a preparation method thereof, wherein the composite membrane comprises a composite hollow fiber membrane and a multi-dimensional hole arranged on the composite hollow fiber membrane, and the preparation method comprises the following steps: placing a polyvinylidene fluoride raw material and a diluent which is 5% of the polyvinylidene fluoride raw material by mass in a reaction kettle, and simultaneously carrying out high-temperature melting; after complete melting, standing and defoaming in a reaction kettle, and spinning after standing for 3-4 h; under the traction of a filament collecting wheel, the spun membrane filaments enter 70% of extraction liquid of polyvinylidene fluoride raw materials in mass ratio for extraction, and are cooled to generate phase separation phenomenon to form pores, so that the composite membrane for the MABR is obtained.

Description

Composite membrane for MABR and preparation method thereof
Technical Field
The invention relates to the technical field of MABR composite membranes, in particular to a composite membrane for MABR and a preparation method thereof.
Background
The membrane-aerated bioreactor (MABR) is a product of the combination of membrane technology and biofilm technology, and supplies oxygen through a permeable membrane, and under the condition that the partial pressure of gas is kept lower than the bubble point, oxygen in a membrane tube cavity penetrates through micropores in the membrane wall to enter the outer side of the tube cavity, so that bubble-free aeration is realized. The bubble-free aeration mass transfer efficiency is high, the oxygen utilization rate can approach 100 percent, and the oxygen utilization rate is 5 to 7 times that of the traditional aeration.
The membrane material of the MABR can be used as a carrier, a microbial membrane can be formed on the membrane surface, oxygen from the inner side of the membrane lumen diffuses from the inside of the biological membrane to the outside, and substrates from sewage diffuse from the surface of the biological membrane to the inside. Because of the anisotropic mass transfer of oxygen and a substrate, the microbial membrane on the membrane component generates an obvious layered structure which is respectively an aerobic layer, a facultative layer and an anaerobic layer from inside to outside. The microbial membrane in the MABR is functionally layered, so that the microbial membrane can independently complete the oxidation and synchronous nitrification-denitrification reactions of organic pollutants in sewage.
The membrane materials suitable for the membrane aeration biofilm reactor can be roughly divided into the following according to the difference of the surface property and the structure: the hydrophobic microporous membrane and the compact nonporous silica gel membrane have the following defects: (1) due to its lower bubble point pressure, the transmission of gas through the membrane pores can easily damage the biofilm layer formed on the membrane surface; (2) in the growth process of the biological membrane, some biological fragments fallen off by cells can be attached to the surface of the membrane and even further block pore channels on the surface, so that the gas mass transfer resistance of the membrane is increased, the gas flux is reduced, and finally the growth of the biological membrane is influenced due to insufficient oxygen supply; (3) such membranes are not suitable for long term operation, as some proteins and biological debris can degrade the hydrophobic properties of the membrane surface leading to liquid ingress into the membrane. Although dense, non-porous silica membranes have certain advantages in bubble point pressure and contamination prevention, their low oxygen flux limits their use in MABR applications.
Therefore, we propose a composite membrane for MABR and a preparation method thereof to solve the above problems.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a composite membrane for MABR and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite membrane for the MABR provided by the invention comprises a composite hollow fiber membrane and a multi-dimensional hole arranged on the composite hollow fiber membrane.
Preferably, the composite hollow fiber membrane is made of vinylidene fluoride.
Preferably, a method for preparing a composite membrane for MABR includes the following steps:
s1: placing a polyvinylidene fluoride raw material and a diluent which is 5 mass percent of the polyvinylidene fluoride raw material in a reaction kettle, simultaneously carrying out high-temperature melting, and controlling the heating temperature to be 120-150 ℃;
s2: keeping the temperature of the reaction kettle at 60-70 ℃ after complete melting, standing in the reaction kettle for defoaming, and starting spinning after standing for 3-4 hours;
s3: under the traction of a yarn collecting wheel, the spun membrane yarn enters 70% of extraction liquid of polyvinylidene fluoride raw materials in mass ratio for extraction, and the membrane yarn is cooled to generate phase separation phenomenon to form pores, so that the composite membrane for MABR is obtained.
Preferably, in S1, the diluent is one or more of acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, n-butanol and styrene.
Preferably, in S1, the polyvinylidene fluoride raw material and the diluent of 5% by mass of the polyvinylidene fluoride raw material are placed in a reaction kettle and melted at a high temperature, and the heating temperature is controlled at 130 ℃.
Preferably, in S2, the temperature of the reaction vessel is maintained at 65 ℃ after the melt is completely melted, the melt is allowed to stand in the reaction vessel for defoaming, and spinning is started after the standing time is 3 hours.
Preferably, in S3, the extract is one or more of alcohol, ether, ketone, ester, amide, thioether, sulfoxide and crown ether.
Preferably, in the S3, the filament collecting speed is 400-500m/min, and the cooling temperature is 30-45 ℃.
Compared with the prior art, in the whole experiment, the properties such as the surface pore form, the membrane wall thickness and the like of the hollow fiber membrane are controlled by controlling the content of polyvinylidene fluoride, the types of diluents and extractants, the heating and standing temperature, the filament collecting rate, the cooling temperature and the like, the surface of the treated composite hollow fiber membrane has higher roughness, the surface of the membrane filament after the doping treatment is rougher than that of the membrane filament after the doping treatment, and the hollow fiber membrane after the doping treatment is more suitable for the attachment growth of microorganisms.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. When "mass, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction. "
The present invention will be further illustrated with reference to the following specific examples.
Example one
The composite membrane for the MABR provided by the invention comprises a composite hollow fiber membrane and a multi-dimensional hole arranged on the composite hollow fiber membrane;
the preparation method comprises the following steps:
s1: placing a polyvinylidene fluoride raw material and a diluent which is 5% of the polyvinylidene fluoride raw material by mass in a reaction kettle, and simultaneously carrying out high-temperature melting, wherein the heating temperature is controlled at 120 ℃;
s2: keeping the temperature of the reaction kettle at 60 ℃ after complete melting, standing in the reaction kettle for defoaming, and starting spinning after standing for 3 hours;
s3: under the traction of a yarn winding wheel, the spun membrane yarn enters 70% of extraction liquid of polyvinylidene fluoride raw materials in mass ratio for extraction, the yarn winding speed is 400m/min, the cooling temperature is 30 ℃, and a pore is formed by cooling and phase separation, so that the composite membrane for the MABR is obtained.
Further, in S1, the diluent is acetone.
Further, in S3, the extract is alcohol.
Example two
The composite membrane for the MABR provided by the invention comprises a composite hollow fiber membrane and a multi-dimensional hole arranged on the composite hollow fiber membrane;
the preparation method comprises the following steps:
s1: placing a polyvinylidene fluoride raw material and a diluent which is 5% of the polyvinylidene fluoride raw material by mass in a reaction kettle, and simultaneously carrying out high-temperature melting, wherein the heating temperature is controlled at 130 ℃;
s2: keeping the temperature of the reaction kettle at 65 ℃ after complete melting, standing in the reaction kettle for defoaming, and starting spinning after standing for 3.5 hours;
s3: under the traction of a yarn winding wheel, the spun membrane yarn enters 70% of extraction liquid of polyvinylidene fluoride raw materials in mass ratio for extraction, the yarn winding speed is 450m/min, the cooling temperature is 35 ℃, and a pore is formed by cooling and phase separation, so that the composite membrane for the MABR is obtained.
Further, in S1, the diluent is acetone.
Further, in S3, the extract is alcohol.
EXAMPLE III
The composite membrane for the MABR provided by the invention comprises a composite hollow fiber membrane and a multi-dimensional hole arranged on the composite hollow fiber membrane;
the preparation method comprises the following steps:
s1: placing a polyvinylidene fluoride raw material and a diluent which is 5% of the polyvinylidene fluoride raw material by mass in a reaction kettle, and simultaneously carrying out high-temperature melting, wherein the heating temperature is controlled at 150 ℃;
s2: keeping the temperature of the reaction kettle at 70 ℃ after complete melting, standing in the reaction kettle for defoaming, and starting spinning after standing for 4 hours;
s3: under the traction of a yarn winding wheel, the spun membrane yarn enters 70% of extraction liquid of polyvinylidene fluoride raw materials in mass ratio for extraction, the yarn winding speed is 500m/min, the cooling temperature is 45 ℃, and a pore is formed by cooling and phase separation, so that the composite membrane for the MABR is obtained.
Further, in S1, the diluent is acetone.
Further, in S3, the extract is alcohol.
Comparative example 1
A preparation method of a composite membrane for MABR comprises the following steps:
s1, preparation of levodopa solution: preparing levodopa into a levodopa solution with the concentration of 0.05-3 g/L;
s2, uniformly coating the levodopa solution on the outer surface of the porous membrane; the pH value of the levodopa solution is 4-11;
s3, the coated porous membrane is subjected to heat treatment to obtain the composite membrane for MABR.
The results of the tests performed on the first to third examples and the first comparative example are as follows:
Figure BDA0002026903040000061
Figure BDA0002026903040000071
in the whole experiment of the invention, properties such as the surface pore form and the membrane wall thickness of the composite hollow fiber membrane after treatment are controlled by controlling the content of polyvinylidene fluoride, the types of diluent and extractant, the heating and standing temperature, the filament collecting rate, the cooling temperature and the like, the surface of the composite hollow fiber membrane after treatment has higher roughness, the surface of the membrane filament after doping treatment is rougher than that of the membrane filament after doping treatment, and the hollow fiber membrane after doping treatment is more suitable for the attachment growth of microorganisms.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (5)

1. The composite membrane for the MABR is characterized by comprising a composite hollow fiber membrane and multidimensional holes arranged on the composite hollow fiber membrane, wherein the composite hollow fiber membrane is made of vinylidene fluoride;
the preparation method of the composite membrane for MABR comprises the following steps:
s1: placing a polyvinylidene fluoride raw material and a diluent which is 5 mass percent of the polyvinylidene fluoride raw material in a reaction kettle, simultaneously carrying out high-temperature melting, and controlling the heating temperature to be 120-150 ℃;
s2: keeping the temperature of the reaction kettle at 60-70 ℃ after complete melting, standing in the reaction kettle for defoaming, and starting spinning after standing for 3-4 hours;
s3: under the traction of a yarn collecting wheel, the spun membrane yarn enters 70% of extraction liquid of the polyvinylidene fluoride raw material by mass ratio for extraction, the cooling is carried out to generate phase separation phenomenon and form holes, the yarn collecting speed is 400-500m/min, and the cooling temperature is 30-45 ℃, thus obtaining the composite membrane for the MABR.
2. The composite membrane for MABR of claim 1, wherein in S1, the diluent is one or more selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, n-butanol and styrene.
3. The composite membrane for an MABR according to claim 1, wherein the diluent in an amount of 5% by mass of the polyvinylidene fluoride raw material and the polyvinylidene fluoride raw material is melted at a high temperature while being placed in a reaction vessel at S1, and the heating temperature is controlled at 130 ℃.
4. The composite film for MABR according to claim 1, wherein said S2, after being completely melted, is kept at a temperature of 65 ℃ in a reaction vessel, and is allowed to stand for defoaming in the reaction vessel, and spinning is started after a standing time of 3 hours.
5. The composite membrane for MABR of claim 1, wherein in S3, said extract is one or more selected from the group consisting of alcohol, ketone, ester, amide, thioether, sulfoxide and crown ether.
CN201910296974.1A 2019-04-15 2019-04-15 Composite membrane for MABR and preparation method thereof Active CN110064309B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910296974.1A CN110064309B (en) 2019-04-15 2019-04-15 Composite membrane for MABR and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910296974.1A CN110064309B (en) 2019-04-15 2019-04-15 Composite membrane for MABR and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110064309A CN110064309A (en) 2019-07-30
CN110064309B true CN110064309B (en) 2021-06-15

Family

ID=67367627

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910296974.1A Active CN110064309B (en) 2019-04-15 2019-04-15 Composite membrane for MABR and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110064309B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111482091B (en) * 2020-05-18 2022-10-21 浙江长兴求是膜技术有限公司 Preparation method of high-performance MABR hollow fiber composite membrane
CN112295419A (en) * 2020-10-20 2021-02-02 淄博蓝景膜环保科技有限公司 Preparation method of selective permeability MABR composite membrane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0734759B1 (en) * 1990-05-09 1999-02-03 USF Filtration Limited Polyvinylidene fluoride membrane
CN106390776A (en) * 2016-08-31 2017-02-15 朱兆奇 Method for producing polyvinylidene fluoride porous membrane with extruder
CN109589803A (en) * 2019-01-28 2019-04-09 北京欧威爱特环保科技有限公司 Microbe carrier hydridization MBfR film and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7338692B2 (en) * 2003-09-12 2008-03-04 3M Innovative Properties Company Microporous PVDF films

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0734759B1 (en) * 1990-05-09 1999-02-03 USF Filtration Limited Polyvinylidene fluoride membrane
CN106390776A (en) * 2016-08-31 2017-02-15 朱兆奇 Method for producing polyvinylidene fluoride porous membrane with extruder
CN109589803A (en) * 2019-01-28 2019-04-09 北京欧威爱特环保科技有限公司 Microbe carrier hydridization MBfR film and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Surface modification of PVDF hollow fiber membrane and its application in membrane aerated biofilm reactor (MABR);Feifei Hou;《Bioresource Technology》;20130423;第140卷;第1-9页 *
氧化石墨烯/聚偏氟乙烯复合膜的制备及抗污;霍霄楠;《环境工程学报》;20170930;第11卷(第9期);第4923-4931页 *

Also Published As

Publication number Publication date
CN110064309A (en) 2019-07-30

Similar Documents

Publication Publication Date Title
CN110064309B (en) Composite membrane for MABR and preparation method thereof
CN101905121B (en) Method for preparing aluminum oxide-based ceramic hollow fibrous membrane
CN108246125B (en) High-anti-pollution internal support polyvinylidene fluoride hollow fiber membrane and preparation method thereof
CN105289319B (en) A kind of preparation method of polymer hollow fiber membrane
CN108744992B (en) Preparation method of flat membrane for sludge concentration
CN108043248B (en) A kind of PVA-PVDF hollow fiber ultrafiltration membrane, preparation method, preparation facilities and application
JP2008237213A (en) Continuous fermentation apparatus
CN107789986A (en) Enhanced hollow fiber ultrafiltration membrane and preparation method thereof
CN109806769B (en) Preparation method of modified graphite-phase carbon nitride material nanofiltration membrane
CN110652888B (en) Low-pressure self-flow polyvinylidene fluoride hollow fiber composite membrane with lining and preparation method thereof
CN113069922A (en) Preparation method of nanofiltration membrane with controllable surface turing structure
KR102115434B1 (en) Ultrahydrophobic composite membrane for a membrane aerated biofilm reactor process and preparation method thereof
JP7359382B2 (en) Hollow fiber membrane, hollow fiber membrane module, wastewater treatment equipment and wastewater treatment method
CN104923093A (en) Hollow fiber ultrafiltration membrane of water purifier and preparation method for hollow fiber ultrafiltration membrane
CN104785123A (en) Hollow fiber ceramic membrane production method
Yang et al. Design and performance study of a novel immobilized hollow fiber membrane bioreactor
CN112569808A (en) Polyvinylidene fluoride mixed matrix membrane with white spirit catalytic filtration performance and preparation and application thereof
CN111744370A (en) Hollow fiber composite membrane, preparation method and application thereof
CN101890309B (en) Method for preparing hollow fiber membranes by using thermally induced phase separation (TIPS) process
CN101890312B (en) Hydrophilic PVDF ultrafiltration membrane and preparation method
CN108854600B (en) Graphene oxide/polyurethane hollow fiber ultrafiltration membrane and preparation method thereof
CN110713253A (en) Bioreactor membrane and preparation process
WO2002094979A2 (en) Production of secondary metabolites
JP5262004B2 (en) Process for producing lactic acid by continuous fermentation
CN112370975A (en) High-strength high-precision MBR (membrane bioreactor) membrane preparation method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant